ES2378320T3 - Two component polyurethane composition with high early mechanical strength - Google Patents

Abstract

Two-component polyurethane composition consists of first component (A) comprising isocyanate-terminated polyurethane prepolymer(s) prepared from polyisocyanate(s) and polyol(s) and second component (B) containing water and polyaldimine(s) obtained from polyamine(s) with aliphatic primary amino groups and low-odor linear, branched, carbocyclic and/or heterocyclic aldehyde(s), optionally with hydroxyl, ether, carboxyl, ester or keto groups. Two-component polyurethane composition consists of first component (A) comprising isocyanate-terminated polyurethane prepolymer(s) prepared from polyisocyanate(s) and polyol(s) and second component (B) containing water and polyaldimine(s) obtained from polyamine(s) with aliphatic primary amino groups and low-odor aldehyde(s) of formula (I) or (II): Y 1>, Y 2>H, OH or substituents; Y 3>, Y 4>substituents . The full definitions are given in the DEFINITIONS (Full Definitions) Field. Independent claims are also included for the following: (1) methods of mixing the composition; (2) method of application of the composition; (3) article sealed with the mixed and cured composition. [Image].

Description

Two component polyurethane composition with high early mechanical strength.

Technical sector

The invention relates to two-component polyurethane compositions, which are suitable as pasty glues, sealing materials and coatings, with a long period of time available for processing, high early mechanical strength, rapid hardening and bubble free , a good adhesion and a small formation of smell when hardening, which is composed of a first component A with isocyanate groups and a second component B, which contains water and at least one polyaldimine.

State of the art

Polyurethane compositions are used, among other uses, for different types of glues, insulations, sealants and coatings. Especially, they are suitable for bonding, insulating or sealing, which require an elasticity of the bonding bond. Polyurethane compositions for elastic bonding are usually pasty doughs and are used as single-component or two-component systems.

A glue suitable for practice must have some special properties. On the one hand, it must guarantee a period of time available for the elaboration sufficiently long (period of useful life and period of open time), so that the user has enough time to apply the glue in the desired places, then place the construction pieces that must be glued and placed correctly. On the other hand, the constitution of mechanical resistance of the glue must be carried out quickly, since for certain uses it is necessary that the glue joint can be subjected to a mechanical load and shortly after the application, for example since the pieces glued construction must be transported to another site, or since an eventual fixation must be eliminated. In order to make such early loads possible on the glue joint, the glue must have a high early mechanical strength, that is to say that the glue joint can be loaded to a certain degree, even before the bond has been fully made. hardening. This also conditions that the glue, in parallel to the rapid constitution of mechanical strength, should also quickly constitute good adhesion to the glued construction pieces, since only then can the bonding joint be subjected to loads. Next, the glue should harden quickly and without the formation of bubbles to achieve its final mechanical strength, so that the elastic bonding joint can be fully loaded as soon as possible. Otherwise, a glue suitable for practice should not cause immersions of strong or unpleasant odors of any kind. In particular, in the case of uses for glue inside closed enclosures, for example in the interior area of buildings or vehicles, a small smell of the materials used is tolerable, since the use of the finished object of elaborate within a reasonable period of time is difficult and even impossible because of strong smell immissions.

Single component polyurethane adhesives are generally not suitable for some uses, which presuppose a high early mechanical strength of the bonding bond. Conditioned by the process of hardening by means of the humidity coming from the air, the hardening and therefore the constitution of mechanical resistance of the glue of a single component are too slow, since the humidity necessary for the reaction of hardening must diffuse from the outside through the layers - which are becoming increasingly thicker - of the hardened material. In addition, single-component polyurethane adhesives that harden quickly tend frequently to bubble during hardening, which significantly disturbs the load-bearing capacity of the bonding bond.

Essentially shorter periods of hardening time are achieved with two component polyurethane adhesives. However, the difficulty is there to find a composition that, after mixing both components, first presents a period of time available for relatively long processing, but then constitutes a high early mechanical strength and quickly hardens. Rapid hardening can be achieved by hardening a component containing isocyanates with a component containing polyamines. This reaction is, however, usually so rapid that it is difficult to achieve a period of time available for manageable processing. In order to slow down the high reactivity of polyamines with isocyanate groups, there are different starting points. For example, special amines can be used, for example, which have aromatic and / or sterically hindered and / or secondary amino groups. Such special amines, however, have certain disadvantages. Aromatic amines, for example, are not toxicologically safe, and sterically hindered amines or amines that have secondary amino groups are generally expensive, lead in part to products with diminished mechanical properties and are often always too reactive, in particularly in combination with the reactive aromatic isocyanate groups.

An additional possibility of deceleration is the addition of polyamide to polyamines in the hardener component, as described in US Pat. US 4,108,842 or US 4,895,883.

US 3,932,357 describes an additional deceleration, when an aldimine is used as a hardening component.

Finally, US 3,420,800 describes polyurethanes, which contain polyisocyanates and bisaldimines and which are hardened by water.

In all these patent documents, aldehydes are predominantly used, which cause an intense odor when applying the respective systems.

Until now there are no known two-component polyurethane compositions that have a long period of time available for processing, high early mechanical strength, rapid and bubble-free hardening, good adhesion and small odor formation when hardening. , which consist of a first component A with isocyanate groups and a second component B, containing water and at least one polyaldimine.

Exhibition of the invention

It is a mission of the present invention to make available a two component polyurethane composition, which has a long period of time available for processing, high early mechanical strength, rapid and bubble free hardening, good adhesion and small formation of smell when hardening.

Surprisingly, it was found that this can be achieved by a two component polyurethane composition, in which the first component A contains at least one polyurethane prepolymer with isocyanate end groups, which is prepared from at least one polyisocyanate and at least one polyol, and in which the second component B contains water and at least one polyaldimine, which is obtainable from at least one polyamine having aliphatic primary amino groups and at least an aldehyde, this aldehyde being poor in smell.

With such a two-component polyurethane composition, for example, pasty glues can be formulated for elastic glues, insulations and sealing, which have a long period of time available for processing, high early mechanical strength, rapid hardening and free of bubbles, Good adhesion and a small odor formation when hardening.

Such a two component polyurethane composition has another interesting property. With the same first component A can be obtained, only by variation of the second component B, with little expense, glues with different mechanical properties, namely adapting the polyamine, used for the preparation of the polyaldimine in the second component B, to the respective requirements. For the glue manufacturer this advantage is of decisive importance. Due to the fact that the first component A remains the same for different glues with different mechanical properties, a great expense disappears for the preparation and packaging of a large number of first components A, whose handling, due to the high sensitivity against the humidity is much more expensive than what happens for the second component B. With the polyurethane composition described above, modified or new requirements in terms of the speed of hardening, to the speed of hardening can be covered tensile strength, elongation at break and the modulus of elasticity, through the recourse that a first component A already present is combined with a second component B that has been optimized for the new requirements.

By using special polyaldimines in the second component B, obtainable from at least one polyamine having aliphatic primary amino groups and at least one odor-poor aldehyde, polyurethane compositions with a small formation of smell during or after total hardening. Thus, the polyurethane compositions described are also suitable for use in enclosures, such as in the interior area of buildings or vehicles.

By combining a polyaldimine and water in the second component B, an optimum reactivity behavior is achieved in common with the first component A. In this way, polyurethane compositions are obtained, which are distinguished by a long period of time available for the elaboration, a high early mechanical resistance and a fast hardening free of bubbles.

With the aid of the present invention, it is also possible to formulate a two-component product system constituted as a construction box (in a modular manner) consisting of a first universal component A and a range of different second components B. With one of such systems can be obtained in a simple manner polyurethane compositions with variously long periods of time available for elaboration, early mechanical strengths, curing rates, a diverse formation of odor when pronouncing the hardening and different mechanical properties.

Way to carry out the invention

The present invention relates to a two component polyurethane composition, which is composed of a first component A containing at least one polyurethane prepolymer A1 with isocyanate end groups, prepared from at least a first polyisocyanate and by at least one polyol, and from a second component B containing water and at least one polyamide B1, which is obtainable from at least one polyamine PA having aliphatic primary amino groups and at least one poor ALD aldehyde in odor, according to formula (I) or formula (II)

In this case, Y1 and Y2 represent, independently of one another, a hydrogen atom, a hydroxyl group or an organic radical; or they form in common a carbocyclic or heterocyclic ring, which has a ring size between 5 and 8, preferably 6, atoms.

Y3 represents either a substituted or unsubstituted alkyl group, which has at least one heteroatom;

or represents a branched or unbranched alkyl or alkylene group with at least 10 C atoms; 15 or represents a substituted or unsubstituted aryl or arylalkyl group;

or represents O-R1 or

R1 in turn representing an aryl, arylalkyl or alkyl group with at least 3 C atoms and in each case being substituted or unsubstituted.

Y4 represents either a substituted or unsubstituted aryl or heteroaryl group having a ring size 20 between 5 and 8, preferably 6, atoms;

or represents , with R2 = alkyl, hydroxyl or alkoxy;

or represents a substituted or unsubstituted alkenyl or arylalkenyl group with at least 6 C atoms.

As "poly" in the terms "polyaldimine", "polyol", "polyisocyanate" and "polyamine" are understood herein as molecules that formally contain two or more of the respective functional groups.

The concept of "polyurethane" encompasses herein all polymers that are prepared according to the polyaddition process with a diisocyanate. This also includes those polymers that are almost or totally free of urethane groups, such as polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurates, polycarbodiimides, etc.

The concept of "polyamine having aliphatic primary amino groups" herein designates always a

30 compounds that formally contain two or more NH2 groups, which are attached to an aliphatic, cycloaliphatic or arylaliphatic radical. They differ in this way from aromatic amines, in which the amino groups are directly linked to an aromatic radical, such as for example in aniline or 2-amino-pyridine.

As a substance "poor in smell" and a substance "with a small formation of smell" means, without establishing differences, a substance whose smell can be perceived, that is to smell, by human individuals only

35 to a small extent, which therefore does not have any intense odor such as, for example, formaldehyde, acetaldehyde, isobutyraldehyde, or solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, and this small smell is not perceived as unpleasant or disgusting by most human individuals.

As a "odor-free" substance is a substance that cannot be smelled by most human individuals, and therefore has no perceptible odor.

The two component polyurethane composition according to the invention contains in the first component A at least one polyurethane prepolymer A1 with isocyanate end groups, prepared from at least one polyisocyanate and at least one polyol.

This reaction can be carried out by means of the reaction that the polyol and the polyisocyanate are reacted with usual procedures, for example at temperatures of 50 ° C to 100 ° C, possibly mediating joint use of appropriate catalysts, the polyisocyanate being dosed in such a way that their isocyanate groups are present in a stoichiometric excess in relation to the hydroxyl groups of the polyol. The excess polyisocyanate is chosen such that in the resulting polyurethane prepolymer A1 there is, after the reaction of all the hydroxyl groups of the polyol, a content of free isocyanate groups of 0.1 to 15% by weight, preferably 0.5 to 5% by weight, based on the entire polyurethane prepolymer A1. Eventually, the polyurethane prepolymer A1 can be prepared by joint use of plasticizing agents, the plasticizers used not containing any reactive groups against the isocyanates.

As polyols for the preparation of polyurethane prepolymer A1, for example, the following commercially available polyols or arbitrary mixtures thereof can be used:

-

poly (oxyalkylene) polyols, also called polyether polyols, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2-2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of an initiating molecule having two or more active hydrogen atoms, such as for example water, ammonia or compounds with various OH or NH groups, such as for example 1,2-ethanediol, 1,2-and 1, 3-propanediol, neopentyl glycol, di (ethylene glycol), tri (ethylene glycol), di (propylene glycols) and tri (propylene glycols) isomers, butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanodiols, decanedioles, decanediols, 1,3-decanedioles, decanedioles, 1,3-decanedioles, decanedioles, 1,3-decanedioles, decanedioles, 1,3-decanediols and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylol-ethane, 1,1,1-trimethylol-propane, glycerol, aniline, as well as mixtures of the aforementioned compounds. Both poly (oxyalkylene) polyols can be used, which have a low degree of unsaturation (measured in accordance with ASTM D-2849-69 and indicated in milliequivalents of unsaturation per gram of polyol (mEq / g)), prepared for example with the help of the so-called double metal cyanide complex catalysts (DMC catalysts = acronym for Double Metal Cyanide) as well as poly (oxyalkylene) polyols having a higher degree of unsaturation, prepared for example with the help of anionic catalysts such as NaOH, KOH or alkali metal alcoholates.

Especially suitable are poly (oxyalkylene) diols or poly (oxyalkylene) triols, in particular poly (oxypropylene) diols or poly (oxypropylene) triols.

Especially suitable are poly (oxyalkylene) diols or poly (oxyalkylene) triols with an unsaturation degree lower than 0.02 mEq / g and with a molecular weight in the range of 1,000 to 30,000 g / mol, as well as poly ( oxypropylene) diols and triols with a molecular weight of 400 to 8,000 g / mol. For the concepts of "molecular weight"

or "molar weight" is understood herein as the weighted average of the molecular weight Mn.

Also especially suitable are poly (oxypropylene) diols or triols called "end capped with OE" (capped at one end with ethylene oxide). The latter are special poly (oxypropylene) poly (oxyethylene) polyols, which are obtained, for example, by means that pure poly (oxypropylene) polyols, after termination of the polypropoxylation, are alkoxylated with ethylene oxide and in this way they have primary hydroxyl groups.

-

Polybutadienes with hydroxy functions

-

Polyester polyols, prepared for example from alcohols from divalent to trivalent, such as for example 1,2-ethanediol, di (ethylene glycol), 1,2-propanediol, di (propylene glycol), 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylol-propane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters, such as for example succinic acid, glutaric acid, adipic acid , subic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid, or mixtures of the aforementioned acids, as well as polyester polyols obtained from lactones such as for example £ -caprolactone.

-Polycarbonate-polyols, as they are accessible by reaction, for example, of the above-mentioned alcohols -employed for the constitution of polyester-polyols -with dialkyl carbonates, diaryl carbonates or phosgene,

-polyacrylate-and polymethacrylate-polyols.

These polyols mentioned have an average molecular weight of 250 to 30,000 g / mol and an average OH functionality in the range of 1.6 to 3.

In addition to these polyols mentioned, low molecular weight di-or multivalent alcohols A1, such as for example 1,2-ethanediol, 1,2- and 1,3-, can be used together in the case of the preparation of the polyurethane prepolymer A1. propanediol, neopentyl glycol, di (ethylene glycol), tri (ethylene glycol), di (propylene glycols), and tri (propylene glycols) isomers, butanediols, hexanediols, heptanediols, octanediols, nonanodiols, decanediols and undechanediols, 1,3-and-dikanediols, 1,3-and-dikanediols, 1,3-and-dikanediols, 1,3-and-dikanedioles, 1,3 4-cyclohexane-dimetanol, hydrogenated bisphenol A, dimer fatty alcohols, 1,1,1-trimethylol-ethane, 1,1-trimethylol-propane, glycerol, pentaerythritol, sugar alcohols and other alcohols of higher valence, alkoxylation products Low molecular weight of the di-and multivalent alcohols mentioned above, as well as mixtures of the aforementioned alcohols.

For the preparation of polyurethane prepolymer A1, commercially available polyisocyanates are used. As examples, the following polyisocyanates optimally known in the polyurethane chemistry should be mentioned:

2,4- and 2,6-toluylenediisocyanate (TDI) and arbitrary mixtures of these isomers, 4,4'-diphenylmethanediisocyanate (MDI), the position isomeric diphenylmethanediisocyanates, 1,3- and 1,4-phenylenediisocyanate, 2,3 , 5,6-tetramethyl-1,4-diisocyanatobenzene, 1,6-hexamethylene diisocyanate (HDI), 2-methyl-pentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1 , 6-hexamethylene diisocyanate (TMDI), 1,12-dodecamethylene diisocyanate, cyclohexane-1,3-and -1,4-diisocyanate and arbitrary mixtures of these isomers, 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane ( = isophorone diisocyanate or IPDI), perhydro-2,4'-and -4,4'-diphenylmethanediisocyanate (HMDI), 1,4-diisocyanate-2,2,6-trimethyl-cyclohexane (TMCDI), my p-xylylenediisocyanate (XDI ), 1,3-and 1,4-tetramethylxylenediisocyanate (TMXDI), 1,3- and 1,4-bis- (isocyanatomethyl) cyclohexane, as well as oligomers and polymers of the aforementioned isocyanates, as well as arbitrary mixtures of isocyanates aforementioned. MDI, TDI, HDI and IPDI are especially preferred.

The first component A has the ability to also harden on its own, that is to say without any contact with the second component B. The isocyanate groups of the first component A can react with moisture, for example from the air, and thus can harden at polymer, analogous to that of a single component polyurethane composition that hardens by moisture. If desired, the reaction of the isocyanate groups with water can be further accelerated, adding to the first component A an appropriate catalyst. Suitable catalysts are, for example, organic tin compounds, such as dibutyl tin dilaurate, dibutyl tin dichloride, dibutyl tin di (acetylacetonate), organic bismuth compounds or complex bismuth compounds, or compounds containing amino groups such as for example 2,2'-dimorpholino-diethyl ether.

In the second component B the two component polyurethane composition according to the invention contains water and at least one polyamide B1.

Polyaldimine B1 can be prepared from at least one PA polyamine having aliphatic primary amino groups and at least one ALD aldehyde by a condensation reaction mediating water separation. Such condensation reactions are optimally known and are described, for example, in the work Houben-Weyl, "Methoden der organischen Chemie" [Methods of organic chemistry], volume XI / 2, pages 73 et seq. In this case it is an equilibrium reaction, the equilibrium being predominantly located on the side of the polyaldimine. This means that when a polyamine having aliphatic primary amino groups is mixed with at least one stoichiometric amount of an aldehyde, the corresponding polyaldimine is formed spontaneously, regardless of whether the water separated during the reaction is removed or not from the reaction mixture. .

As polyamines PA having aliphatic primary amino groups for the preparation of polyamide B1, polyamines known in the chemistry of polyurethanes, such as, inter alia, are used for two component polyurethanes. As examples, the following should be mentioned:

ethylenediamine, 1,2- and 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3- and 1,4-butanediamine, 1,3- and 1 , 5-pentanediamine, 1,6-hexamethylenediamine, 2,2,4-and 2,4,4-trimethylhexamethylene diamine and mixtures thereof, 1,7-heptanediamine, 1,8-octanediamine, 4-aminomethyl-1,8- octanediamine, 1,9-nonanodiamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, methyl-bis- (3-amino-propyl) amine, 1,5-diamino-2-methyl-pentane (MPMD ), 1,3-diaminopentane (DAMP), 2,5-dimethyl-1,6-hexamethylenediamine, cycloaliphatic polyamines such as 1,2-, 1,3- and 1,4-diamino-cyclohexane, bis- (4- amino-cyclohexyl) -methane, bis (4-amino-3-methyl-cyclohexyl) methane, bis- (4-amino-3-ethyl-cyclohexyl) -methane, bis- (4-amino-3,5-dimethyl- cyclohexyl) -methane, 1-amino-3-aminomethyl3,5,5-trimethyl-cyclohexane (= isophoronadiamine or IPDA), 2-and 4-methyl-1,3-diamino-cyclohexane and mixtures thereof, 1,3 and 1 , 4-bis (aminomethyl) -cyclohexane, 1-cyclohexylamino-3-amino-propane, 2,5 (2,6) -bis- (aminomethyl) -bicyclo [2.2.1] h eptane (NBDA), prepared by Mitsui Chemicals), 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.02.6] decane, 1,4-diamino2,2,6-trimethyl-cyclohexane ( TMCDA), 3,9-bis- (3-amino-propyl) -2,4,8,10-tetraoxaespiro [5.5] undecane, 1,3- and 1,4-xylylenediamine, aliphatic polyamines containing ether groups, such as bis- (2-amino-ethyl) -ether, 4,7-dioxadecane1,10-diamine, 4,9-dioxadodecane-1,12-diamine and higher oligomers thereof, poly (oxyalkylene) -polyamines which theoretically have two or three amino groups, obtainable for example under the name of Jeffamine® (prepared by Huntsman Chemicals), as well as mixtures of the aforementioned polyamines.

Preferred polyamines PA are 1,6-hexamethylenediamine, MPMD, DAMP, 2,2,4- and 2,4,4-trimethylhexamethylene diamine, 4-aminomethyl-1,8-octanediamine, IPDA, 1,3- and 1,4 -xilylenediamine, 1,3- and 1,4-bis- (aminomethyl) cyclohexane, bis- (4-amino-cyclohexyl) -methane, bis- (4-amino-3-methyl-cyclohexyl) -methane, 3 (4 ), 8 (9) -bis- (aminomethyl) tricycle [5.2.1.02.6] decane, 1,2-, 1,3- and 1,4-diamino-cyclohexane, 1,4-diamino-2,2, 6-trimethyl-cyclohexane,

5 poly (oxyalkylene) -polyamines which theoretically have two or three amino groups, in particular Jeffamine® EDR-148, Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® T-403, as well as in particular mixtures of two or more of the polyamines mentioned above.

The polyaldimine B1 contained in the composition according to the invention is obtainable from at least one PA polyamine having aliphatic primary amino groups and from at least one ALD aldehyde, this being

10 aldehyde poor in smell. An essential feature of the invention is that the aldehyde is poor in smell.

In a first embodiment, ALD aldehydes of the following formula (I) are used:

Y1 and Y2 represent, on the one hand, independently of each other, a hydrogen atom, a hydroxyl group or an organic radical. On the other hand Y1 and Y2 can be linked together to form a carbocyclic or heterocyclic ring, having a ring size between 5 and 8, preferably 6, atoms.

For Y3 four possibilities are presented: Y3 may represent a substituted or unsubstituted alkyl group, which has at least one heteroatom, in in particular in the form of an ether oxygen, a carboxyl group, an ester group or a hydroxyl group.

20 Y3, however, may also represent a branched or unbranched alkyl or alkylene group with at least 10 C atoms. In addition, Y3 may also represent a substituted or unsubstituted aryl or arylalkyl group.

Finally, Y3 can also represent a radical of the formula O-R1 or

R 1, meanwhile, represents an aryl, arylalkyl or alkyl group with at least 3 C atoms, and each case being substituted or unsubstituted.

Examples of compounds according to formula (I) are:

decanal, dodecanal; ethers based on 2-hydroxy-2-methyl-propanal and alcohols such as propanol, isopropanol, butanol and 2-ethyl-hexanol; esters based on 2-formyl-2-methyl-propionic acid and alcohols such as propanol, isopropanol, butanol and 2-ethyl-hexanol; esters based on 2-hydroxy-2-methyl-propanal and carboxylic acids such

30 as butyric acid, isobutyric acid and 2-ethyl-hexanoic acid; aldoses such as for example glycerol-aldehyde, erythrose or glucose; 2-phenyl-acetaldehyde, 2-phenyl-propionaldehyde (hydropic aldehyde); as well as the aldehydes set forth below as particularly appropriate.

Particularly suitable, on the one hand, are compounds according to formula (III)

35 representing R3 and Y5, independently of one another, a hydrogen atom or an alkyl or arylalkyl group and Y1 and Y2 having the meanings already described.

As examples of compounds of the formula (III) there should be mentioned 3-hydroxy-pivalaldehyde, 3-hydroxy-2-methyl

propionaldehyde, 3-hydroxy-propionaldehyde, 3-hydroxy-butyraldehyde, 3-hydroxy-valeraldehyde; � -hydroxy-aldehydes, such

as formed from a cross-aldol reaction from formaldehyde and aldehydes such as 2-methyl40 butyraldehyde, 2-ethyl-butyraldehyde, 2-methyl-valeraldehyde, 2-ethyl-capronaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2, 3,6-tetrahydro-benzaldehyde, 2-methyl-3-phenyl-propionaldehyde, 2-phenyl-propionaldehyde (hydratropic aldehyde), diphenyl-acetaldehyde; as well as ethers based on such -hydroxy-aldehydes and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethyl-hexanol or fatty alcohols, such as for example 3-methoxy- and 3-ethoxy-y 3-propoxy-y 3-isoproxy-y 3-butoxy-as well as 3- (2-ethyl-hexoxy) -2,2-dimethyl-propanal.

Particularly suitable, on the other hand, are compounds according to formula (IV):

having Y1, Y2 and R3 the meanings already described, and

Y6 representing a hydrogen atom or an alkyl or arylalkyl or aryl group, optionally with at least one heteroatom, in particular with at least one ether oxygen, and optionally with at least one group

10 carboxyl, and possibly with at least one ester group, or a linear or branched hydrocarbon chain, unsaturated once or multiple times.

Examples of preferred aldehydes of the formula (IV) are the products of an esterification from the aforementioned hydroxyaldehydes, such as 3-hydroxy-pivalaldehyde, 3-hydroxy-isobutyraldehyde, 3-hydroxy-propionaldehyde, 3-hydroxy-butyraldehyde , 3-hydroxy-valeraldehyde, 2-hydroxymethyl-2-methyl-butyraldehyde, 2-hydroxymethyl-2-ethyl

15 butyraldehyde, 2-hydroxymethyl-2-methyl-valeraldehyde, 2-hydroxymethyl-2-ethyl-hexanal, 1-hydroxymethyl-cyclopentanecarbaldehyde, 1-hydroxymethyl-cyclohexane-carbaldehyde, 1-hydroxymethyl-cyclohex-3-ene-carbaldehyde, -hydroxymethyl-2-methyl-3-phenyl-propionaldehyde, 3-hydroxy-2-methyl-2-phenyl-propionaldehyde and 3-hydroxy-.2,2-diphenyl-propionaldehyde with carboxylic acids such as formic acid, acetic acid, propionic acid , butyric acid, isobutyric acid, 2-ethyl-caproic acid and benzoic acid, as well as the aldehydes set forth below as especially preferred.

In an especially preferred embodiment, ALD aldehydes of the formula (IV) are used, which are odor-free and whose radicals R3 and Y6 are restricted as follows:

R3 represents a hydrogen atom, and

Y6 represents, on the one hand, a linear or branched alkyl chain with 11 to 30 carbon atoms, possibly with at least one heteroatom, in particular with at least one ether oxygen,

25 or represents a linear or branched hydrocarbon chain, unsaturated once or multiple times, with 11 to 30 carbon atoms,

or represents a radical of the formula (V) or (VI)

In formulas (V) and (VI) R4 represents a linear or branched or cyclic alkylene chain with 2 to 16 atoms

30 carbon, possibly with at least one heteroatom, in particular with at least one ether oxygen. or represents a linear or branched or cyclic unsaturated hydrocarbon chain once or multiple times with 2 to 16 carbon atoms,

and R6 represents a linear or branched alkyl chain with 1 to 8 carbon atoms, and

Y1 and Y2 have the meanings that have already been described.

35 The dashed line in formulas (V) and (VI) designates in each case the binding site.

This embodiment of the invention makes it possible to prepare not only polyurethane compositions with a small odor formation, but also to prepare those that are totally without noticeable odor. This is especially advantageous for uses in the interior of buildings and vehicles.

Examples of these aldehydes of formula IV, odor-free (= toilets), especially preferred, which in polyurethane compositions do not cause any noticeable odor, are esterification products based on the aforementioned hydroxy-aldehydes, such as 3 -hydroxy-pivalaldehyde, 3-hydroxy-isobutyraldehyde, 3-hydroxypropanal, 3-hydroxy-butyraldehyde, 3-hydroxy-valeraldehyde, 2-hydroxymethyl-2-methyl-butyraldehyde, 2-hydroxymethyl-2-ethyl5 butyraldehyde, 2-hydroxymethyl 2-methyl-valeraldehyde, 2-hydroxymethyl-2-ethyl-hexanal, 1-hydroxymethyl-cyclopentanecarbaldehyde, 1-hydroxymethyl-cyclohexane-carbaldehyde, 1-hydroxymethyl-cyclohex-3-eno-carbaldehyde, 2-hydroxymethyl-2-methyl-3- phenyl-propionaldehyde, 3-hydroxy-2-methyl-2-phenyl-propionaldehyde and 3-hydroxy-2,2-diphenyl-propionaldehyde, with carboxylic acids such as for example lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, acid palmitic, margaric acid, stearic acid, á nonadecanoic acid, araicic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, elewestric acid, arachidonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, subic acid, azelaic acid, sebacic acid, acid 1 , 12-dodecanedioic acid, maleic acid, fumaric acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3,6,9-trioxa-undecanedioic acid and similar derivatives of poly (ethylene glycols), dehydrogenated ricinoleic acids, as well as fatty acids from technical scale saponification of natural oils and fats, such as by

15 example rapeseed oil, sunflower oil, flaxseed oil, oilseed oil, coconut nut oil, oilseed oil and oilseed oil.

Preferred carboxylic acids are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, succinic acid, adipic acid, azelaic acid and sebacic acid and technical mixtures of fatty acids, which contain these acids.

In a preferred method of preparing an ALD aldehyde of the formula (IV), a -hydroxy-aldehyde, for example one of the aforementioned -hydroxy-aldehydes, such as 3-hydroxy-pivalaldehyde, which can be prepared for example starting from formaldehyde (or paraformaldehyde) and isobutyraldehyde, possibly in situ, it can be reacted with a carboxylic acid, in particular with a long chain fatty acid, to give the corresponding ester, namely with a Y6-COOH carboxylic acid to give the corresponding carboxylic acid ester of

25 for example 3-hydroxy-pivaldehyde; and / or with a monoalkyl ester of HOOC-R4-COOR5 dicarboxylic acid to give the aldehyde of the formula (IV) with the radical Y6 according to the formula (VI); and / or with a HOOC-R4-COOH dicarboxylic acid to give the aldehyde of the formula (IV), in this case a dialdehyde, with the radical Y6 according to the formula (V). The formulas (V) and (VI) and Y6, R4 and R5 have in this case the meanings already described. This esterification can be carried out without the use of solvents according to known methods, as described for example in the work Houben-Weyl, "Methoden der organischen Chemie", volume VIII, pages 516-528.

In the case of the use of carboxylic acids, a mixture based on the aldehydes of the formula (IV) with the radicals Y6 according to the formula (V) and according to the formula (VI) is obtained, when for example it is first esterified a part of the carboxylic acid groups with a -hydroxy-aldehyde, for example 3-hydroxy-pivalaldehyde, and then the remaining carboxylic acid groups are esterified with an alkyl alcohol (R5-OH). A

The mixture can subsequently be used directly for the preparation of polyaldimine B1.

Suitable carboxylic acids intended for esterification with a -hydroxy-aldehyde, for example 3-hydroxy-pivalaldehyde are, for example, the short-chain and long-chain carboxylic acids that have already been mentioned.

In another embodiment, ALD aldehydes of the following formula (II) are used:

Y4 may represent, on the one hand, a substituted or unsubstituted aryl or heteroaryl group, having a ring size between 5 and 8, preferably 6, atoms.

On the other hand, Y4 can represent a radical of the formula

, R 2 representing, in turn, an alkyl, hydroxyl or alkoxy group.

Finally Y4 may represent a substituted or unsubstituted alkenyl or arylalkenyl group, which has at least 6 C atoms.

Examples of aldehydes according to formula (II) are benzaldehyde, 2-and 3-and 4-tolualdehyde, 4-ethyl-and 4-propyl-and 4isopropyl-and 4-butyl-benzaldehyde, salicylaldehyde, 2,4-dimethyl-benzaldehyde , 2,4,5-trimethyl-benzaldehyde, 4-acetoxybenzaldehyde, 4-anisaldehyde, 4-ethoxy-benzaldehyde, di-and tri-alkoxy-benzaldehyde isomers, vanillin, ovainillin, 2-and 4-carboxy-benzaldehyde, 4 -dimethylamino-benzaldehyde, 2-, 3-and 4-nitro-benzaldehyde, 2-and 3-and 4-formylpyridine, 2-furfuraldehyde, 2-thiophenecarbaldehyde, 1-and 2-naphthylaldehyde, 3-and 4-phenyloxy-benzaldehyde , quinoline-2-carbaldehyde and its positional isomers in 3, 4, 5, 6, 7 and 8, anthracene-9-carbaldehyde, phthalaldehyde, isophthalaldehyde, terephthaldehyde, as well as glyoxalic acid, methyl ester of glyoxalic acid and cinnamic aldehyde.

Benzaldehyde, 4-dimethylamino-benzaldehyde, 3-and 4-phenyloxy-benzaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, glyoxalic acid and cinnamic aldehyde are preferred.

The reaction of at least one PA polyamine having aliphatic primary amino groups with at least one ALD aldehyde of the formula (I) or the formula (II) results, for example, B1 polyaldimines of the schematic formulas (VII), (VIII ) and (IX)

representing n 2, 3 or 4 and representing Q the radical of a polyamine having aliphatic primary amino groups, after removal of all primary amino groups; Y

10 representing m an integer from 0 to 10, and the Qs in the same molecule being the same or different and in each case must represent the radical of a polyamine having aliphatic primary amino groups after the elimination of all primary amino groups. The radicals Y1, Y2, Y3, Y4, Y6 and R4 in the formulas (VII),

(VIII) and (IX) have the meanings already described.

If a dialdehyde of the formula (IV) with the radical Y6 according to the formula (V) is used for the preparation of a

15 polyaldimine B1, this is used advantageously or in a mixture with a monoaldehyde of the formula (IV), and certainly in a quantitative relationship such that for polyaldimine B1 according to the formula (IX) about m on average are obtained values in the range of 1 to 10; or the dialdehyde according to formula (IV) is added dosed in such a way that an excess of aldehyde groups is present in relation to the amino groups in the case of the preparation of the polyaldimine B1, the excess of aldehyde being chosen such that

20 for the polyaldimine B1 of the formula (IX), values in the range of 1 to 10 are also obtained on average. With both types, a mixture of oligomeric polyaldimines with a well manageable viscosity is obtained.

As a polyaldimine B1, mixtures of different polyaldimines can also be used, in particular mixtures of different polyaldimines, prepared with the help of different PA polyamines which are also reacted.

25 have aliphatic primary amino groups, with different or equal ALD aldehydes of the formula (I) or (II). It may also be absolutely advantageous to prepare mixtures of polyamide B1, using mixtures of PA polyamines with different numbers of aliphatic primary amino groups.

For the preparation of polyaldimine B1, the aldehyde groups of the aldehyde ALD are used in a stoichiometric amount or in a stoichiometric excess in relation to the primary amino groups of the polyamine PA.

Usually, the polyaldimine B1 of the second component B is used in an excess lower than the stoichiometric referred to the isocyanate groups of the prepolymer A1 of the first component A, and certainly in an amount of 0.1 to 0.99 equivalents of aldimine groups per equivalent of isocyanate groups, in particular in an amount of 0.4 to 0.8 equivalents of aldimino groups for each equivalent of isocyanate groups.

Otherwise, water is present in the second component B. The amount of water, which is necessary for a total hardening of the polyurethane composition can be calculated using the following formula:

(mole of water) = (Eq of aldimine) + [(Eq of NCO) - (Eq of aldimine)] / 2 (X) in which "Eq" represents "equivalent", "aldimine" represents "aldimine groups "And" NCO "represents" isocyanate groups. "

The second component B must not contain exactly the amount of water that is necessary for the hardening of the first component A according to formula (X). It may contain, for example, a greater amount of water, for example double or more, or less water of the second component B may be present than is calculated using the formula (X). In this case, the remaining water necessary for hardening can be collected from the humidity of the air. It is advantageous that at least the amount of water that is necessary for the total transformation of the polyaldimine into the polyamine is present in the second component B. This means that the second component B preferably contains at least as many moles of water as equivalents of aldimine groups are present, or, expressed in another way: The second component B preferably has at least one water molecule per Each aldimino group.

Water may be present in the second component B or in the form of free water, or it may be fixed to a support material. However, the fixation must be reversible, which means that the water must be accessible, after mixing both components A and B, for the reaction with the aldimino groups and the isocyanate groups.

Appropriate support materials for component B may be hydrates or complexes with Aquo, in particular inorganic compounds having the water fixed in a coordinative manner or as crystallization water. Examples of such hydrates are Na2SO4 · 10 H2O, CaSO4 · 2 H2O, CaSO4 · ½ H2O, Na2B4O7 · 10 H2O, MgSO4 · 7 H2O.

Other suitable support materials are porous materials, which enclose water in the hollow spaces. In particular, these are special silicates and zeolites. Especially suitable are kieselgur (diatomaceous earth) and molecular sieves. The size of the hollow spaces must be chosen in such a case that they are optimal for water collection. Therefore, molecular sieves having a pore size of 4 Å are shown as especially suitable.

Other suitable support materials are those that collect water in non-stoichiometric amounts and have a pasty consistency or form gels. These support materials may be inorganic or organic in nature. Examples thereof are silica gels, clays such as montmorillonite, bentonites and hectorite, or polysaccharides such as celluloses and starches, or poly (acrylic acids) and poly (acrylonitriles) which are also known within the concept of "super-absorbents" and which are used for example in hygiene items. Otherwise, support materials bearing ionic groups are suitable. As support materials, polyurethane polymers with carboxyl groups or sulfonic acid groups are especially preferred as side chains, and respectively their salts, in particular their ammonium salts. These support materials can absorb water and fix it until the water collection capacity has been exhausted.

Especially preferred polyurethane polymers with carboxyl groups or sulfonic acid groups as side chains, and respectively their salts, can be obtained for example from polyisocyanates and polyols, which contain groups of carboxylic acids or sulfonic acids. The acid groups can then be neutralized, for example in the fully reacted state, with bases, in particular tertiary amines. The properties of the support material are greatly dependent on the polyols and functional polyisocyanates that are used. In particular, attention should be paid to hydrophilicity or respectively to hydrophobicity of the isocyanates and polyols chosen. It has been shown that especially short chain polyols provide very suitable support materials.

The following auxiliary agents and additives well known in the polyurethane industry may be present in the polyurethane compositions described above:

Plasticizing agents, for example esters of organic carboxylic acids or their anhydrides, phthalates, such as for example dioctyl phthalate or diisodecyl phthalate, adipates, such as for example dioctyl adipate, sebacate, esters of phosphoric and organic sulfonic acids, polybutenes and other compounds that do not react with isocyanates; reactive diluting agents and crosslinking agents, for example plurivalent alcohols, polyamines, polyaldimines, polythymimines or aliphatic isocyanates such as, for example, 1,6-hexamethylene diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6 -hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and arbitrary mixtures of these isomers, 1-isocyanate-3,3,5-triethyl-5-isocyanatomethyl-cyclohexane (= isophorone diisocyanate or IPDI), Perhydro-2,4'-and -4,4'-diphenylmethanediisocyanate, 1,3- and 1,4-tetramethyl-xylylenediisocyanate, isocyanates of these isocyanates, oligomers and polymers of these isocyanates as well as their adducts with polyols; inorganic and organic fillers, such as, for example, ground or precipitated calcium carbonates, which are optionally coated with stearates, in particular a finely divided coated calcium carbonate, carbon blacks, kaolins, aluminum oxides, silicic acids and powders or hollow spheres of PVC (polyvinyl chloride); fibers, for example based on polyethylene; pigments, catalysts, such as for example organic tin compounds such as dibutyl tin dilaurate, dibutyl tin dichloride, di (acetylacetonate) ) of dibutyl-tin, organic bismuth compounds or complex compounds of bismuth, or compounds containing amino groups, such as for example 2,2'-dimorpholino-diethyl ether, or other catalysts common in the chemistry of polyurethanes for reaction of isocyanate groups; otherwise, catalysts for the hydrolysis of polyaldimine, such as for example organic carboxylic acids such it is as benzoic acid or salicylic acid, an organic carboxylic acid anhydride such as phthalic acid anhydride or hexahydrophthalic acid anhydride, a silyl ester of organic carboxylic acids, an organic sulfonic acid such as ptoluenesulfonic acid or 4-dodecyl benzenesulfonic acid, or other organic or inorganic acids, or mixtures of the aforementioned acids; rheology modifying agents, such as for example thickening agents, for example urea compounds, polyamide waxes, bentonites, or pyrogenic silicic acids; adhesion mediating agents, in particular silanes such as epoxy silanes, vinyl silanes, isocyanate silanes and amino silanes that have reacted with aldehydes to form aldimino silanes, as well as oligomeric forms of these silanes; drying agents, such as for example p-tosyl isocyanate and other reactive isocyanates, orthoesters of formic acid, calcium oxide or molecular sieves; stabilizing agents against heat, and against the irradiation of light and UV rays, substances that inhibit the flame (flame retardants); substances with surface activity, such as for example wetting agents, equalizing agents, deaerating agents or antifoaming agents; fungicides or substances that inhibit the growth of fungi; as well as other substances that are usually used in the polyurethane industry, making it clear to a person skilled in the art if these additional substances are to be appropriate as additives for both components or only for one of the two components A and B.

The two-component polyurethane composition according to the invention also allows the formulation of white compositions, which harden quickly and without the formation of bubbles. It is known that white systems, which harden with water, often show strong bubble formation, since these systems do not contain any carbon black, which can partially suppress the formation of bubbles in black systems.

The preparation and storage of the two components, in particular of the first component A, is carried out by means of moisture exclusion. The two components are stable in storage separately from each other, that is, they can be stored in an appropriate container or in an appropriate arrangement, such as in a barrel, a bag or a cartridge, before use, during several months for up to a year and longer, without them losing their aptitude for use. In one embodiment, the second component B can be stored in a container as described below, which is integrated in an overlapping dosage supplement.

It is also possible that the two components are packaged and stored in separate containers from each other through separation walls. Examples of such containers are coaxial cartridges or twin cartridges.

It may be advantageous to adapt each other to the consistencies of the two components A and B, since pastes having a similar consistency can be mixed more easily.

The present invention makes it possible to formulate two component polyurethane compositions that are completely free of organic solvents (VOC acronym for Volatile Organic Compounds = volatile organic compounds). This is especially advantageous for ecological and occupational hygiene reasons.

The mixing of both components A and B is advantageously carried out continuously during the application. In a possible embodiment, the mixing of the two components A and B can be carried out by means of a higher dosage supplement containing two dosing rotors that engage with each other. Such preferred higher dosage supplements are described in detail in European patent document EP 0 749 530. The upper dosage supplement is preferably placed for smaller uses, on a commercially available cartridge, containing the first component A, while that the second component B is inside a container that is integrated in the upper dosage supplement. The dosing and mixing are carried out, in the case of the application in this upper dosing supplement, which is operated passively by means of the loading with pressure of the cartridge, for example by means of the cartridge press that is usual in the trade. For a better thorough mixing, a static mixer can also be placed next to the outlet opening of this upper dosing supplement.

An additional possibility for mixing the two components A and B is the so-called twin cartridges or the so-called commercial coaxial cartridges, in each case with a static mixer placed next to the outlet hole. In the case of the use of twin cartridges, the two components A and B are located inside separate cartridges, attached one next to the other, which flow into a common outlet hole. The application is carried out by means of an appropriate juicer device, which squeezes parallel to both cartridges. In the case of the use of coaxial cartridges, one of the two components is located in the cartridge core. The other component surrounds it, the components being separated by a coaxial wall. The two components are squeezed at the same time when the application is also carried out by means of an appropriate juicer device and they flow into a common outlet hole.

For industrial uses, on the other hand, a transport of the two components A and B from barrels or barrels with flange cover is advantageously used. In this case the two components A and B are advantageously mixed with an upper dosage supplement that differs essentially from the higher dosage supplement described above in the fact that it has a hose connection for the second component B.

The mixing of the two components A and B of the polyurethane composition is carried out essentially in a homogeneous manner or essentially layer by layer. An essentially homogeneous mixture is preferred. If the two components A and B are essentially mixed layer by layer, for example working with a static mixer that has a very small number of mixing elements, then, after total hardening, a homogeneous product hardened in its mass results , in which the original layers are no longer visible. This circumstance is surprising to one skilled in the art, rather it would have been expected that in the case of an introduction and mixing layer by layer of polyaldimines in a polyurethane composition containing isocyanates result in the boundaries between layers some areas that are not they harden correctly, which therefore remain soft, since there the ratio of aldimino groups to isocyanate groups is manifestly superior to the stoichiometric one. Usually, isocyanate-containing polyurethane compositions, in fact, do not harden properly, when they come into contact with a stoichiometric excess of polyamine hardening agents. The fact that components A and B also harden by essentially mixing layer by layer to give a homogeneous product, in practice has a great advantage, since also in the case of an essentially homogeneous mixing process small heterogeneities can always appear .

The mixing ratio between the first component A and the second component B can be chosen fundamentally freely, but a mixing ratio A: B in the range of 200: 1 to 5: 1 in parts by volume is preferred.

A typical application is made by first mixing the two components A and B of the polyurethane composition as described, and then contacting the mixed polyurethane composition with at least one surface of a solid body and hardening it. The contact with the surface of a solid body is typically carried out in the form of an application of a track on the surface.

When the two components A and B are mixed, the hydrolyzed form of polyaldimine B1 reacts with the isocyanate groups, a reaction formally taking place between amino groups and isocyanate groups; then, at least partially, the polyurethane composition hardens. As already mentioned above, the balance in the second component B between, on the one hand, the aldimine groups and water and, on the other hand, the amino groups and the aldehyde, is located strongly towards the side of the aldimino groups. and of the water. When, however, the second component B is contacted with the first component A, then the amino groups formally react with the isocyanate groups to form urea groups, whereby the equilibrium is constantly shifted in the direction of the amino groups. In this way, the formal reaction between the polyaldimine B1 of the second component B and the isocyanate groups of the first component A proceeds in a total way. The excess isocyanate groups react either with the water that is additionally present in the second component B or with the water that is collected from the air (air humidity), which ultimately leads to the total hardening of the polyurethane composition.

The reaction of the polyurethane prepolymer containing isocyanate A1 groups with the polyaldimine B1 to be hydrolyzed should not necessarily be carried out through the polyamine. Obviously, reactions with intermediate stages of the hydrolysis of the polyaldimine to form the polyamine are also possible. For example, it can be conceived that the polyaldimine to be hydrolyzed reacts directly in the form of a semi-terminal directly with the polyurethane prepolymer containing A1 isocyanate groups.

As a consequence of the reactions described above, the polyurethane composition hardens.

The aldehydes used for the preparation of polyamide B1 are released upon hardening. By using the special ALD aldehydes according to formula (I) or formula (II), only a small odor is noticeable in this case. In a particularly preferred embodiment, the ALD aldehydes used are distinguished by the fact that, because of their low vapor pressure, they remain in the hardened polyurethane composition, and that they do not cause any noticeable odor . In the case of the use of long chain fatty acids, the hydrophobic fatty acid results in a smaller absorption of water by the hardened polyurethane composition, which increases the hydrolysis stability of the polyurethane material. In addition, a hydrophobic fatty acid radical in the case of a contact with water that lasts longer, offers good protection against the extraction by washing of the aldehydes from the hardened polyurethane composition. These polyurethane compositions also have good stability against light.

The polyurethane compositions that have been described are distinguished by a long period of time available for processing, a high early mechanical strength, a rapid and bubble free hardening and a small odor formation, both before, during, and after of hardening. They exhibit extremely good adhesion on various surfaces of solid bodies, which, because of the very rapid hardening, constitutes absolutely no evidence, since rapidly hardening polyurethane compositions tend, according to experience, to weakening in the constitution of accession. The two-component polyurethane composition, fully hardened, has a high elongation or high expansion and high tensile strength. By varying, for example, the amount and type of polyaldimine B1 and the amount of water referred to the amount of isocyanate groups, the period of time available for processing can be varied, as well as the influence of constitution of early mechanical strength and hardening speed.

With the polyurethane compositions that have been described, it is possible to formulate a two-component product system constituted as a construction box (modularly), which is composed of a first universal component A and a range of different second components B. Depending on the requirements of an application, component B that is optimally appropriate can be combined with component A - always left unchanged -. With one of such systems, polyurethane compositions can be obtained in a simple manner with periods of time available for the elaboration of different duration, early mechanical resistances, hardening speeds, a diverse formation of odor when pronouncing the hardening and some various mechanical properties, without component A having to be formulated again. This constitutes a great advantage, for example, for a glue manufacturer, since it is essentially more favorable that the first moisture-sensitive component A can be produced in large quantities in an invariable formulation.

The polyurethane composition described above is suitable as glue for bonding, insulating and sealing various substrates, for example for the bonding of construction parts in the production and manufacture of automobiles, rail vehicles, ships or other industrial goods, as material. of sealing of any type, for example for the sealing of joints in the construction, as well as as a coating or coating for various articles or respectively for various surfaces of variable solid bodies.

As coatings, layers of protective paints, seals, protective coatings and primer coatings are preferred. Among the coatings, floor coverings are especially preferred. Such coatings can be produced by typically pouring and equalizing a reactive composition onto the substrate, where it hardens to form a floor covering. For example, such floor coverings are used for offices, housing areas, hospitals, schools, warehouses, parking garages and other private or industrial uses. Since these uses are carried out over a large area, an insignificant release of substances from the coating can lead to difficulties in occupational hygiene and / or odor discomfort, even if it is a use in the outdoor sector. However, a large part of the coatings are applied in the interior sector, which is why a small odor formation is given special importance here.

The polyurethane composition is contacted at least partially with the surface of an arbitrary substrate. Uniform contacting in the form of a sealing or glue material, of a coating or of a coating is preferred, and certainly in areas where for use they need a joint in the form of a glue or a seal, or however whose substrate must be covered. It may be absolutely necessary that the substrate or respectively the article to be contacted can be subjected, prior to contacting, to a prior physical and / or chemical treatment, for example by grinding, sandblasting , brushing or similar operations, or by treatment with cleaning agents, solvents, adhesion mediating agents, solutions of adhesion mediating agents or primers, or the application of an adhesion bridge or a sealing agent (in English sealer).

Examples

All the data in so many percent refer, where nothing else is indicated, to so many percent by weight.

Polyamines used

An alpha, omega-poly (oxypropylene) diamine (Jeffamine® D-230, from Huntsman):

Total content of primary amines � 97%; Amines content = 8.22 mmol of NH2 / g.

1,3-xylylenediamine (MXDA; from Mitsubishi Gas Chemical):

MXDA content � 99%; amine content = 14.56 mmol of NH2 / g.

Polyols used

Acclaim® 4200 N (from Bayer): A linear poly (propylene oxide) polyol with a theoretical OH functionality of 2, an average molecular weight of approximately 4000, an OH number of approximately 28 mg KOH / g, and an unsaturation degree of approximately 0.005 mEq / g.

Caradol® MD34-02 (from Shell): A poly (propylene oxide) -poly (ethylene oxide) polyol, terminated in ethylene oxide with a theoretical OH functionality of 3, with an average molecular weight of approximately 4,900, a OH index of approximately 35 mg KOH / g, and an unsaturation degree of approximately 0.08 mEq / g.

Description of test methods

The open time period, that is the maximum possible time period, in which the glue, after application, can still be made. for example by brush extension or by pressing against a solid body surface or an article to be glued -, it was determined with the help of two criteria, namely consistency and adhesion, and certainly as follows. The glue was applied in the form of a triangular caterpillar with a width of approximately 1 cm on a sheet of LDPE (low density polyethylene) and then the caterpillar was covered at regular intervals of time, each time with a glass insert, which before of use had previously been treated with a Sika® activating agent (obtainable from Sika Schweiz AG) and had been ventilated for 10 minutes. Then, the glass insert was pressed by a traction machine (from Zwick) without loss of time until it reached a thickness of 5 mm and was marked or inscribed with the time elapsed between the application of the track and the incorporation by pressing of the insert. The force required for pressing was recorded. As soon as the pressing force exceeded 3 N, the open time period was declared as terminated. Additionally, in the test tube bodies that had been pressed within the open time period the adhesion of the glue track was tested, hardening the test tube bodies for one day at 23 ° C and with a relative air humidity of 50% and then removing the glue from the glass. The last of the glass inserts, which still showed a fully cohesive adhesion frame, indicated the open time period. The shortest of the two determined open time periods is exposed in each case.

The early mechanical resistance was determined as follows. For each test, two glass inserts with the dimensions 40 x 100 x 6 mm on the side to be glued were previously treated with a Sika® activating agent (obtainable from Sika Schweiz AG). After a ventilation period of 10 minutes, the glue was applied in the form of a triangular track parallel to the longitudinal edge on one of the glass plates. After approximately one minute, the glue applied was pressed using the second glass insert using a traction machine (from Zwick) until it reached a glue thickness of 5 mm (corresponding to a glue width of approximately 1 cm ), and then stored at 23 ° C and with a relative air humidity of 50%. In this way, 3 test specimens were produced 5 times, realizing that after different time intervals, depending on the hardening speed of the composition, in each case three of the glued glass plates were stretched with a tensile speed of 200 mm / min. and the maximum force for this was recorded in N / mm of track length and averaged across the three samples. For each composition the early mechanical strength was determined, therefore, after several periods of hardening time.

The period of time until a tensile strength of 1 MPa is achieved is also a measure of early mechanical strength. He was determined by the tensile test described previously. For this, a tensile strength diagram was developed based on the period of hardening time, from which the period of time was read until a tensile strength of 100 N / cm (corresponding to a mechanical resistance of 1 MPa with a glue width of 1 cm).

Tensile strength and elongation at break were determined in films hardened for 7 days at 23 ° C and with a relative humidity of 50% with a layer thickness of 2 mm, in accordance with DIN EN 53504 (speed of traction: 200 mm / min.).

Shore A hardness was determined in accordance with DIN 53505.

The formation of bubbles was assessed qualitatively with the aid of the amount of bubbles, which appeared during the hardening of the films used for mechanical tests (tensile strength and elongation of breakage).

The odor of the compositions was assessed by smelling with the nose at a distance of 10 cm next to the films used for mechanical tests (tensile strength and elongation of breakage) for 1 hour after application at 23 ° C and humidity 50% relative air.

The viscosity was measured at 20 ° C in a cone and plate viscometer of the Haake entity (PK100 / VT-500).

a) Preparation of polyaldimines

Polyaldimine PA1

In a round bottom flask with a reflux coolant and a water separating device (Dean Stark), 40.5 g of formaldehyde (37% in water, methanol-free), 36.0 g of isobutyraldehyde were weighed in, 100.0 g of lauric acid and 1.0 g of 4-toluene sulfonic acid and placed under a nitrogen atmosphere. The mixture was heated in an oil bath with vigorous stirring, after which water began to separate. After four hours, the equipment was put into a vacuum in the vacuum of a water tube. A total of about 35 ml of a distilled material was collected in the separator device. The reaction mixture was cooled, and 48.6 g of Jeffamine® D-230 was added from a dropping funnel. After this, the volatile components were completely removed by vacuum distillation. The liquid reaction product at room temperature, obtained in this way, had an aldimine content, determined as an amine content of 2.17 mmol of NH2 / g, a viscosity at 20 ° C of 700 MPa · s and had no odor perceptible.

Polyaldimine PA2

As described for the polyaldimine PA1, 40.5 g of formaldehyde (37% in water, methanol-free), 36.0 g of isobutyraldehyde, 100.0 g of lauric acid and 1.0 g of 4-toluene-sulfonic acid mediating 35 ml of water separation, and the reaction mixture obtained in this case was combined with 26.0 g of MXDA. After removal of the volatile components in vacuo, a liquid reaction product was obtained at room temperature, which had an aldimine content, determined as an amine content, of 2.33 mmol of NH2 / g and had no detectable odor.

Polyaldimine PA3

In a round bottom flask, 50.0 g of finely pulverized 3-hydroxy-pivalaldehyde (in dimer form) were suspended in 100 ml of water, placed under a nitrogen atmosphere and heated in an oil bath at 60 ° C. From a drip funnel 59.6 g of Jeffamine® D-230 were added dropwise over 30 minutes, after which a clear pale yellow solution was obtained. After this, volatile components were completely removed by vacuum distillation. The pale yellow liquid reaction product at room temperature, obtained in this way, had an aldimine content, determined as an amine content, of 4.86 mmol of NH2 / g and had a weak amine odor.

Polyaldimine PA4

In a round bottom flask, 16.3 g of glucose monohydrate was dissolved in 50 ml of water, combined with 0.05 g of p-toluenesulfonic acid and placed under a nitrogen atmosphere. From a drip funnel, 10.0 g of Jeffamine® D-230 was added dropwise, after which a clear, pale yellow solution was obtained. After this, volatile components were completely removed by vacuum distillation. The yellow brown viscous liquid reaction product at room temperature, obtained in this way, had an aldimine content, determined as an amine content, of 3.52 mmol of NH2 / g and had no perceptual odor.

Polyaldimine PA5

In a round bottom flask, 25.0 g of ground 4-dimethylaminobenzaldehyde was suspended in 100 ml of ethanol, and placed under a nitrogen atmosphere. From a drip funnel, 19.4 g of Jeffamine® D-230 were slowly added dropwise, after which a clear yellow solution was obtained. After this, volatile components were completely removed by vacuum distillation. The viscous liquid reaction product at room temperature, dark yellow, obtained in this way, had an aldimine content, determined as an amine content, of 3.84 mmol NH2 / g and had a weak aromatic odor.

PA6 polyaldimine

As described for polyaldimine PA5, 25.0 g of 3,4,5-trimethoxybenzaldehyde were reacted with 14.8 g of Jeffamine® D-230. After removal of the volatile components in vacuo, a yellow viscous liquid reaction product at room temperature was obtained, having an aldimine content, determined as an amine content, of 3.23 mmol of NH2 / g It had a faint aromatic smell.

Polyaldimine PA7 (for comparison)

In a round bottom flask 50.0 g of Jeffamine® D-230 were previously placed, and placed under a nitrogen atmosphere. With good cooling and vigorous stirring, 32.6 g of isobutyraldehyde were added from a dropping funnel. After this, volatile components were completely removed by vacuum distillation. The liquid reaction product at room temperature, obtained in this way, had an aldimine content, determined as an amine content, of 5.81 mmol of NH2 / g and had a strong aldehyde odor.

b) Preparation of the first component A

Example 1 (component A)

In a vacuum mixer, 3,400 g of an A1 polyurethane prepolymer were prepared, the preparation of which is described below, 1,402 g of diisodecyl phthalate (DIDP), 14 g of p-tolylsulfonyl isocyanate (TI® additive agent from Bayer), 21 g of 3-glycidoxypropyltrimethoxysilane (Silquest® A-187, from OSi Crompton), 1,052 g of calcined kaolin, 1,052 g of carbon black and 7 g of di-n-butyl-tin dichloride (1.8% in DIDP) mediating exclusion of moisture, to give a homogeneous paste free of lumps, and were preserved mediating exclusion of moisture. The material had an isocyanate group content of 0.241 mmol of NCO / g and a density of 1.23 g / cm3.

After total hardening of the first component A only by the humidity of the air at 23 ° C and with an air humidity of 50%, it had

a Shore A hardness of 47,

a tensile strength of 7.4 MPa and

a breaking elongation of 310%.

The polyurethane prepolymer A1 was prepared as follows:

10 1,290 g of Acclaim® 4200 N polyol, 2,580 g of Caradol® MD34-02 polyol, 630 g of 4,4'-methylene diphenyldiisocyanate (MDI, Desmodur® 44 MC L, from Bayer) and 500 g of DIDP were reacted from according to a known process at 80 ° C to give a polyurethane prepolymer terminated in NCO. The reaction product had a content, determined by titration, of free isocyanate groups of 2.07% by weight and a viscosity at 20 ° C of 56 Pa.s.

15 c) Preparation of the second components B

Example 2 to 17 (component A)

In a vacuum mixer the components indicated in Tables 2a and 2b were mixed mediating moisture exclusion, and were prepared to give a lump-free homogeneous paste, which was preserved mediating moisture exclusion.

The density of components B according to Examples 2 to 17 corresponded to that of component A according to Example 1, except for Examples 5 and 14.

In Tables 2a and 2b "DIDP" represents diisodecyl phthalate, "DOA" represents dioctyl adipate and "kaolin" represents a calcined kaolin. "Cat. tin ”represents a solution of 1.8% di-n-butyl tin dichloride in DIDP.

"Cetimine" in Table 2b and in Table 7 designates polythymimine obtained from 3,3,5-trimethyl-5-aminomethylcyclohexylamine (IPDA) and methyl ethyl ketone. It was prepared as described in US Pat. US 4,108,842 as "hardening agent 1". She had a ketimine content, determined as an amine content, of 3.37 mmol of NH2 / g, and had a pungent and intense smell of solvent.

Table 2a: Composition in parts by weight of the second components B Table 2b: Continuation of Table 2

Example

2 3 4 5 6 7 8 9

PA1

44.5 55.6 66.7 95.1 66.6 66.7 -

PA2

- - - - - - 62.1 -

PA3

- - - - - - - 29.8

Salicylic acid

0.3 0.3 0.3 0.4 0.3 0.3 0.3 -

Water

3.0 3.3 3.5 4,5 2.6 4.3 3.5 3.5

DIDP

22.0 10.6 - - 0.2 - 3.9 36.5

Pyrogen silicic acid

2.0 2.0 2.0 - 2.0 2.0 2.0 2.0

Kaolin

28.2 28.2 27.5 - 28.2 26.7 28.2 28.2

Example

10 eleven 12 13 14 Ref. * 15 Ref. * 16 Ref. * 17 Ref. *

PA1

- - - 76.6 - - - -

PA4

41.1 - - - - - - -

PA5

- 37.7 - - - - - -

PA6

- - 44.8 - - - - -

PA7

- - - - 27.9 - - -

Ketimine

  - - - - 42.9 - -

Di (propylene glycol)

- - - 7.4 - - - 9.7

Salicylic acid

0.3 1.0 1.0 0.3 0.2 0.2 - -

Water

3.5 3.5 3.5 3.0 3.5 3.5 4.3 -

DIDP

- 27.6 20.5 - 38.2 23.2 65.5 59.1

DOA

24.9 - - - - - - -

Pyrogen silicic acid

2.0 2.0 2.0 12.7 2.0 2.0 2.0 2.0

Kaolin

 28.2 28.2 28.2 - 28.2 28.2 28.2 28.2

Tin Cat

- - - - - - - 1.0

* Ref. = comparison

d) Preparation and testing of hardened compositions

For the preparation of hardened compositions, the first component A according to Example 1 was mixed with the respective second component B in the volume ratio of 10: 1.

The mixing of the two components A and B was carried out continuously during the application, the two components being applied from a coaxial polyethylene cartridge for two 1:10 components of the Mixpak entity with a static mixer placed on top of the Sulzer Quadro type with 24 mixing elements. For Example 19 (second component B according to Example 5) 36 mixing elements were used, since

10 that the second component B according to Example 5 did not contain any of the loading materials and therefore it was more difficult to incorporate and mix in the first component A.

Table 3: Examples 18 to 21

Example

18 19 twenty twenty-one

Component A according

Ex.1 Ex.1 Ex.1 Ex.1

Component B according

Ex 2 Ex 3 Ex 4 Ex 5

Polyaldimine in component B

PA1 PA1 PA1 PA1

NH2 / NCO

0.4 0.5 0.6 0.7

H2O / NCO

0.70 a) 0.75 a) 0.80 a) 0.85 a)

Open time period (min.)

40 35 25 10

Early mechanical resistance after 180 min. (N / cm)

9 17 78 120

Example

18 19 twenty twenty-one

Period of time to achieve a tensile strength of 1 MPa (min.)

360 300 200 160

Tensile strength (MPa)

6.5 6.7 6.4 6.8

Breaking Elongation%

430 460 460 480

Shore A

46 44 44 Four. Five

Bubble formation

any any any any

Odor

none None none none

a) exactly the amount of water that is necessary to achieve total hardening of component A according to the formula (X) defined above is present.

Examples 18 to 21 have different amounts of polyaldimine PA1. The ratio of NH2 / NCO (that is, equivalents of aldimine groups of the second component B for each equivalent of isocyanate groups of the first

5 component A) varies from 0.4 / 1 to 0.7 / 1. The amount of water in these mixtures, indicated as H2O / NCO (that is, moles of water for each equivalent of isocyanate groups) is dosed in each case such that the water is exactly enough to fully hydrolyze the polyaldimine and harden to the remaining isocyanate groups of the polyurethane prepolymer.

With an increasing content of polyaldimine also increases early mechanical resistance, while

10 correspondingly decreases the period of time until a tensile strength of 1 MPa is achieved. The open time period also decreases. The mechanical properties of the hardened compositions, the tensile strength and the elongation of breakage, show, despite a different polyaldimine content, only small differences. In the case of hardening in all four Examples, neither bubbles nor a noticeable smell appear.

Table 4: Examples 22 and 23 in comparison with Example 20 a) exactly the amount of water that is necessary to achieve total hardening of component A according to the formula (X) defined above is present.

Example

22 twenty 2. 3

Component A according

Ex.1 Ex.1 Ex.1

Component B according

Ex 6 Ex 4 Ex 7

Polyaldimine in component B

PA1 PA1 PA1

NH2 / NCO

0.6 0.6 0.6

H2O / NCO

0.6 b) 0.8 a) 1.0 c)

Open time period (min.)

40 25 10

Early mechanical resistance after 180 min. (N / cm)

3. 4 78 150

Period of time to achieve a tensile strength of 1 MPa (min.)

450 200 140

Tensile strength (MPa)

6.2 6.4 6.4

Breaking Elongation (%)

450 460 420

Shore A

44 44 Four. Five

Bubble formation

any any any

Example

22 twenty 2. 3

Odor

none none none

b) only the amount of water that is necessary for the hydrolysis of polyaldimine is present,

5 The remaining NCO groups need moisture from the air for hardening.

c) more water is present than would be necessary for the total hardening of Component A.

Examples 20, 22 and 23 have a constant content of polyaldimine PA1, but different amounts of water. In such a case it can be seen that an elevation of the water content leads to an acceleration, both in the case of

10 open time period as in the one of the early mechanical resistance and the period of time until a tensile strength of 1 MPa is achieved. Tensile strength and elongation at break show hardly any differences. When hardening in all three examples, neither bubbles nor a noticeable smell appeared.

Table 5: Example 24 compared to Example 20

Example

twenty 24

Component A according

Ex.1 Ex.1

Component B according

Ex 6 Ex 4

Polyaldimine in component B

PA1 PA1

NH2 / NCO

0.6 0.6

H2O / NCO

0.8 0.8

Open time period (min.)

25 twenty

Early mechanical resistance after 120 min. (N / cm)

40 230

Early mechanical resistance after 180 min. (N / cm)

78 n.d.

Period of time up to a tensile strength of 1 MPa (min.)

200 85

Tensile strength (MPa)

6.4 6.2

Breaking Elongation (%)

460 400

Shore A

44 52

Bubble formation

any any

Odor

none none

15 “n.d.” represents “not determined”

Example 24 is differentiated from Example 20 by the polyaldimine used, the same aldehyde having been reacted in each case with two different polyamines. The different amines certainly had no great influence on the mechanical properties of the final product, with greater reason, however, on the development of early mechanical resistance: In the case of a similar open time period, mechanical resistance

Early in Example 24 it is constituted essentially faster than in Example 20. Both Examples have neither bubbles when hardening nor a noticeable odor.

Table 6: Examples 25 to 29 compared to Example 20

Example

twenty 25 26 27 28 29

Component A according

Ex.1 Ex.1 Ex.1 Ex.1 Ex.1 Ex.1

Component B according

Ex 4 Ex 9 Ex 10 Ex 11 Ex 12 Ex 13

Polyaldimine in component B

PA1 PA3 PA4 PA5 PA6 PA1

NH2 / NCO

0.6 0.6 0.6 0.6 0.6 0.6

H2O / NCO

0.8 0.8 0.8 0.8 0.8 0.8

Open time period (min.)

25 5 fifty 10 fifteen twenty

Early mechanical resistance after 120 min. (N / cm)

40 n.d. 35 n.d. 170 Four. Five

Early mechanical resistance after 180 min. (N / cm)

78 n.d. 140 n.d. n.d. n.d.

Period of time to achieve a tensile strength of 1 MPa (min.)

200 twenty 170 twenty 80 180

Tensile strength (MPa)

6.4 5.3 5.6 5.2 5.1 6.1

Breaking Elongation (%)

460 490 280 450 450 480

Shore A

44 36 49 42 40 42

Bubble formation

any any any any any any

Odor

none none none

"N.d." represents "not determined"

Examples 25 to 28 are differentiated from Example 20 by the polyaldimine used, the same polyamine having been reacted with different aldehydes. The open time periods as well as the early mechanical resistances are very different. Example 25 is a very fast system. Because of the existing OH groups next to the aldehyde, the hardened material is softer than in Example 20, since a part of the isocyanate groups does not cross-link with the humidity of the air, but reacts with these OH groups. Example 26 has a long open time period of 50 min., But in the case of the development of early mechanical resistance it is manifestly faster than in Example 20. This is an interesting combination for practice. Aldehyde

The separated one has several OH groups, and therefore can react with a part of the isocyanate groups and thus contribute to hardening. Example 29 contains, in addition to PA1, still di (propylene glycol); the properties are similar to as in the case of Example 20.

All Examples did not form bubbles upon hardening. Examples 25, 27 and 28 had a small smell, while the other Examples had no noticeable smell.

15 Examples 20 to 29 are a demonstration that it is possible to obtain a modular system that is composed of a component A and different components B, which differ manifestly in terms of the time periods available for processing, Early mechanical strengths, hardening speeds, odor as well as mechanical properties, and therefore can be adapted to the requirements of different uses.

20 Comparative Examples 30 (which separates isobutyraldehyde) and 31 (which separates methyl ethyl ketone) both have a very high reactivity, which leads to an undesirably short open time period. The respective mixture, when hardening is not acceptable for the mentioned uses.

Comparative Example 32, which hardens only through water in component B, certainly has an acceptable reactivity and has no noticeable odor, but many bubbles are formed when hardening, which is not acceptable for said uses.

Comparative Example 33, which hardens through a polyol, certainly has an acceptable reactivity, has no odor and does not have bubbles, but the surface of the hardened composition remains, however, very sticky, since, because of the similar reactivity of water from air humidity and di (propylene glycol) with isocyanate groups, a part of the polymer chains located next to the surface does not harden properly (chain interruptions occur)

Table 7: Comparative examples 30 to 33

Example

30 Ref * 31 Ref * 32 Ref * 33 Ref *

Component A according

Ex.1 Ex.1 Ex.1 Ex.1

Component B according

Ex 4 Ex 9 Ex 10 Ex 11

Hardener in component B

PA7 water Cetimine, water just water Di (propylene glycol)

NH2 / NCO

0.6 / 1 0.6 / 1 - -

H2O / NCO

- - - 0.6 / 1

NH2 / NCO

0.8 / 1 0.8 / 1 1/1 -

Open time period (min.)

0.5 1.5 fifteen 25

Early mechanical resistance after 30 min. (N / cm)

fixed fixed n.d. n.d.

Early mechanical resistance after 120 min. (N / cm)

n.d. n.d. 90 42

Period of time up to a tensile strength of 1 MPa (min.)

8 25 125 210

Tensile strength (MPa)

6.5 7.2 7.2 5.5 *

Breaking Elongation (%)

440 400 330 500 *

Shore A

44 47 46 35 *

Bubble formation

any any many any

Odor

very strong very strong none none

"N.d." represents "not determined" "Ref." Represents "comparison"

* The hardened composition has a very sticky surface.

Claims (26)

1. Two-component polyurethane composition, which is composed of a first component A comprising at least one polyurethane prepolymer A1 with isocyanate end groups, prepared from at least one polyisocyanate and at least one polyol and of a second component B comprising Water as well as at least one polyamide B1, which is obtainable from at least one polyamine PA that it has aliphatic primary amino groups and at least one odor aldehyde, poor in odor, according to the formula (I) or formula (II) realizing that Y1 and Y2 O well independently of each other, they represent a hydrogen atom, a hydroxyl group 15 or an organic radical; or in common they represent a carbocyclic or heterocyclic ring, which has a ring size between 5 and 8, preferably 6, atoms. and Y3 20 or represents a substituted or unsubstituted alkyl group, which has at least one heteroatom; or represents a branched or unbranched alkyl or alkylene group with at least 10 C atoms; or represents a substituted or unsubstituted aryl or arylalkyl group; or represents O-R1 or R1 representing an aryl, arylalkyl or alkyl group with at least 3 C atoms and in each case being substituted or unsubstituted. and Y4 or it represents a substituted or unsubstituted aryl or heteroaryl group having a ring size between 5 and 8, preferably 6, atoms; or It represents , with R2 = alkyl, hydroxyl or alkoxy; 5th represents an alkenyl or arylalkenyl group substituted or unsubstituted with at least 6 C atoms. 2. Two component polyurethane composition according to claim 1, characterized in that the Heteroatom in Y3 is in the form of an ether oxygen, a carboxyl group, an ester group or a hydroxyl group. 3. Two component polyurethane composition according to claim 1, characterized in that the ALD aldehyde has the formula (III), 15 representing R3 and Y5, independently of one another, a hydrogen atom or an alkyl or arylalkyl group 4. Two component polyurethane composition according to claim 1, characterized in that the ALD aldehyde has the formula (IV), realizing that 20 R3 has the meanings already described, and Y6 O well represents a hydrogen atom; or 25 represents an alkyl or arylalkyl or aryl group, which optionally has at least one heteroatom, optionally contains at least one carboxyl group, and optionally contains at least an ester group; or 30 represents a linear or branched hydrocarbon chain, unsaturated once or multiple times. 5. Two component polyurethane composition according to claim 4, characterized in that R3 represents a hydrogen atom, as well as Y6 O well represents a linear or branched alkyl chain with 11 to 30 carbon atoms, possibly with at least one heteroatom, in particular with at least one ether oxygen; or represents a linear or branched unsaturated hydrocarbon chain once or multiple times with 11 up to 30 carbon atoms; or represents a radical of the formula (V) or (VI), realizing that R4 or represents a linear, branched or cyclic alkylene chain with 2 to 16 carbon atoms, possibly with at least one heteroatom, in particular with at least one ether oxygen; or represents a linear or branched or cyclic unsaturated hydrocarbon chain once or multiple times with 2 to 16 carbon atoms; Y R5 represents a linear or branched alkyl chain with 1 to 8 carbon atoms. 6. Two-component polyurethane composition according to one of claims 4 or 5, characterized in that the ALD aldehyde, used for the preparation of the polyaldimine, is obtainable by an esterification reaction of a -hydroxy-aldehyde with a carboxylic acid , in particular without the use of any solvent, 25 -hydroxy-aldehyde being prepared in situ from formaldehyde or paraformaldehyde, and a second aldehyde. 7. Two component polyurethane composition according to claim 6, characterized in that the ALD aldehyde used for the preparation of the polyaldimine is obtainable by an esterification reaction of 3-hydroxy-pivalaldehyde with a carboxylic acid, in particular without the use of any solvent, being The 3-hydroxy-pivalaldehyde prepared in situ from formaldehyde or paraformaldehyde, and isobutyraldehyde, respectively. 8. Two-component polyurethane composition according to claim 6 or 7, characterized in that the carboxylic acid used for the preparation of the ALD aldehyde is selected from the group comprising lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid , linoleic acid, linolenic acid, acid 35 succinic, adipic acid, azelaic acid and sebacic acid, their mixtures as well as their technical mixtures with fatty acids.

9.

 Two component polyurethane composition according to one of the preceding claims, characterized in that Y1 = Y2 are = methyl.

10.

 Two component polyurethane composition according to claim 1 or 2, characterized in that the aldehyde ALD has the formula (I) and Y1 represents a hydroxyl group, Y2 represents a hydrogen atom and Y3 represents an alkyl group with at least one hydroxyl group, in particular with more than one hydroxyl group.

eleven.

 Two component polyurethane composition according to one of the preceding claims, characterized in that the polyamine PA having primary amino groups is selected from the group consisting of 1,6-hexamethylenediamine, MPMD, DAMP, 2,2,4- and 2,4,4-trimethyl-hexamethylenediamine, 4-aminomethyl-1,8octanediamine, IPDA, 1,3- and 1,4-xylylenediamine, 1,3- and 1,4-bis- (aminomethyl) cyclohexane, bis- (4-amino-cyclohexyl) methane, bis- (4-amino-3-methyl-cyclohexyl) -methane, 3 (4), 8 (9) -bis- (aminomethyl) -tricyclo [5.2.1.02.6] decane , 1,2-, 1,3- and 1,4-diamino-cyclohexane, 1,4-diamino-2,2,2,6-trimethyl-cyclohexane, poly (oxyalkylene) -polyamines which theoretically have two or three amino groups, in particular Jeffamine® EDR-148, Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® T403, as well as mixtures of two or more of the aforementioned polyamines.

12.

 Composition of two component polyurethane according to one of the preceding claims, characterized in that for the preparation of polyaldimine B1, the aldehyde ALD is used in a stoichiometric amount or in a stoichiometric excess in relation to the primary amino groups of the polyamine PA .

13.

 Two component polyurethane composition according to one of the preceding claims, characterized in that the water is presented in the second component B in free form or reversibly attached to a support material.

14.

 Two component polyurethane composition according to one of the preceding claims, characterized in that the second component B has at least one water molecule for each aldimine group.

fifteen.

 Two component polyurethane composition according to one of the preceding claims, characterized in that the polyol for the preparation of the polyurethane prepolymer A1 of the first component A has an average OH functionality of 1.6 to 3.

16.

 Two-component polyurethane composition according to claim 15, characterized in that the polyol is a poly (oxyalkylene) -polyol, in particular a poly (oxyalkylene) -diol or -triol, more particularly a poly (oxypropylene) diol-o -triol, or a poly (oxypropylene) -diol or -triol capped at the ends with OE (ethylene oxide).

17.

Two component polyurethane composition according to claim 15 or 16, characterized in that the polyol is a poly (oxyalkylene) polyol with an unsaturation degree of <0.02 mEq / g and a weight average molecular weight Mn of 1,000 to 30,000 g / mol

18.

 Two component polyurethane composition according to claim 17, characterized in that the polyol is a polyol prepared by DMC catalysis.

19.

 Composition of two component polyurethane according to one of the preceding claims, characterized in that the polyurethane prepolymer A1 in the first component A and the polyaldimine B1 in the second component B are presented in the ratio of 0.1 to 0.99, in particular 0.4 to 0.8 equivalents of aldimino groups for each equivalent of isocyanate groups.

twenty.

 Process for mixing a two component polyurethane composition according to one of claims 1 to 19, characterized in that the first component A and the second component B are essentially mixed in a homogeneous manner.

twenty-one.

 Process for mixing a two component polyurethane composition according to one of claims 1 to 19, characterized in that the first component A and the second component B are essentially mixed layer by layer.

22

 Procedure for mixing according to claim 20 or 21, characterized in that the mixing of the two components A and B is carried out by means of a higher dosage supplement, which contains two dosing rotors that engage with each other, as well as possibly additionally by means of a static mixer placed next to the exit orifice of this upper dosing supplement.

2. 3.

 Method for the application of a two component polyurethane composition according to one of claims 1 to 19, characterized in that it comprises the following steps:

-

mix the two components A and B,

-

contacting at least one surface of a solid body with the mixed polyurethane composition,

-

harden the mixed polyurethane composition.

24.

 Method for the application according to claim 23, characterized in that the contact with the surface of a solid body is carried out in the form of an application of a track on the surface.

25.

 Use of a two component polyurethane composition according to one of claims 1 to 19, as a glue, a sealing material or a coating, in particular as a glue or a sealing material.

26.

Article, which is continuously connected with force with a two-component polyurethane composition mixed and hardened, according to one of claims 1 to 19.